Definition of the Subject
Silicon is environmentally benign and ubiquitous. Because of its high specific capacity, it is considered one of the most promising candidates to replace the conventional graphite negative electrode used in today’s Li-ion batteries. The theoretical specific capacity of silicon is 4,212 mAh/g (Li22Si5) [1], which is 10 times greater than the specific capacity of graphite (LiC6, 372 mAh/g). However, the high specific capacity of silicon is associated with large volume changes (more than 300%) when alloyed with lithium . These extreme volume changes can cause severe cracking and disintegration of the electrode and lead to significant capacity loss. Significant scientific research has been conducted to circumvent the deterioration of silicon-based anode materials during cycling. Various strategies, such as reduction of particle size, generation of active/inactive composites, fabrication of silicon-based thin films, use of...
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Abbreviations
- Li-ion battery:
-
A family of rechargeable batteries in which lithium ions move from the negative electrode to the positive electrode during discharge, and back to the anode when charging.
- Electric vehicle:
-
Vehicle propelled by an electric motor (or motors) powered by rechargeable battery packs.
- PHEV:
-
Plug-in hybrid electrical vehicle. This is a hybrid vehicle with rechargeable batteries that can be restored to full charge by connecting a plug to an external electric power source.
- Nanowire:
-
A nanowire is a nanostructure, with the diameter of the order of a nanometer and aspect ratio greater than 10:1.
- CVD:
-
Chemical vapor deposition.
- HEMM:
-
High-energy mechanical milling.
- Coulombic efficiency:
-
The efficiency with which charge (electrons) is transferred in a system facilitating an electrochemical reaction.
- Specific capacity:
-
Capacity per unit weight of a battery (Ah/kg or mAh/g).
- Specific energy:
-
Energy per unit weight of a battery (Wh/kg).
- Energy density:
-
Energy per unit volume of a battery (Wh/l).
Bibliography
Boukamp BA, Lesh GC, Huggins RA (1981) All-solid lithium electrodes with mixed-conductor matrix. J Electrochem Soc 128:725–729
Dey AN (1971) Electrochemical, alloying of lithium in organic electrolytes. J Electrochem Soc 118:1547–1549
Tirado JL (2003) Inorganic, materials for the negative electrode of lithium-ion batteries: state-of-the-art and future prospects. Mater Sci Eng R Rep 40:103–136
Winter M, Besenhard JO (1999) Electrochemical lithiation of tin and tin-based intermetallics and composites. Electrochim Acta 45:31–50
Kim I-S (2003) Synthesis, structure and properties of electrochemically active nanocomposites. Ph.D thesis, Carnegie Mellon University
Sharma RA, Seefurth RN (1976) Thermodynamic properties of the lithium-silicon system. J Electrochem Soc 123:1763–1768
van der Marel C, Vinke GJB, van der Lugt W (1985) The phase diagram of the system lithium-silicon. Solid State Commun 54:917–919
Lai S-C (1976) Solid lithium-silicon electrode. J Electrochem Soc 123:1196–1197
Li H et al (2000) The crystal structural evolution of nano-Si anode caused by lithium insertion and extraction at room temperature. Solid State Ionics 135:181–191
Limthongkul P, Jang Y-I, Dudney NJ, Chiang Y-M (2003) Electrochemically-driven solid-state amorphization in lithium-silicon alloys and implications for lithium storage. Acta Mater 51:1103–1113
Limthongkul P, Jang Y-I, Dudney NJ, Chiang Y-M (2003) Electrochemically-driven solid-state amorphization in lithium-metal anodes. J Power Sources 119–121:604–609
Maranchi JP, Hepp AF, Kumta PN (2003) High capacity reversible silicon thin film anodes lithium ion batteries. Electrochem Solid-State Lett 6:A198–A201
Ryu JH, Kim JW, Sung Y-E, Oh SM (2004) Failure modes of silicon powder negative electrode in lithium secondary batteries. Electrochem Solid-State Lett 7:A306–A309
Li J, Dahn JR (2007) An in situ x-ray diffraction study of the reaction of Li with crystalline Si. J Electrochem Soc 154:A156–A161
Obrovac MN, Christensen L (2004) Structural changes in silicon anodes during lithium insertion/extraction. Electrochem Solid-State Lett 7:A93–A96
Hatchard TD, Dahn JR (2004) In situ XRD and electrochemical study of the reaction of lithium with amorphous silicon. J Electrochem Soc 151:A838–A842
Datta MK, Kumta PN (2009) In situ electrochemical synthesis of lithiated silicon-carbon based composites anode materials for lithium ion batteries. J Power Sources 194:1043–1052
Wang W, Kumta PN (2010) Nanostructured hybrid silicon/carbon nanotube heterostructures: reversible high-capacity lithium-ion anodes. ACS Nano 4:2233–2241
Obrovac MN, Krause LJ (2007) Reversible cycling of crystalline silicon powder. J Electrochem Soc 154:A103–A108
Beaulieu LY, Eberman KW, Turner RL, Krause LJ, Dahn JR (2001) Colossal reversible volume changes in lithium alloys. Electrochem Solid-State Lett 4:A137–A140
Park MH et al (2009) Silicon nanotube battery anodes. Nano Lett 9:3844–3847
Datta MK, Kumta PN (2006) Silicon and carbon based composite anodes for lithium ion batteries. J Power Sources 158:557–563
Sandia National Laboratories. Sandia National Laboratories News Releases. Sandia National Laboratories, Livermore, CA, 6 March 2003
Kasavajjula U, Wang C, Appleby AJ (2007) Nano- and bulk-silicon-based insertion anodes for lithium-ion secondary cells. J Power Sources 163:1003–1039
Larcher D et al (2007) Recent findings and prospects in the field of pure metals as negative electrodes for Li-ion batteries. J Mater Chem 17:3759–3772
Timmons A et al (2007) Studies of Si[sub 1 – x]C[sub x] electrode materials prepared by high-energy mechanical milling and combinatorial sputter deposition. J Electrochem Soc 154:A865–A874
Huggins RA (1999) Lithium, alloy negative electrodes. J Power Sources 81–82:13–19
Mao O et al (1999) Active/inactive nanocomposites as anodes for Li-ion batteries. Electrochem Solid-State Lett 2:3–5
Weydanz WJ, Wohlfahrt-Mehrens M, Huggins RA (1999) A room temperature study of the binary lithium-silicon and the ternary lithium-chromium-silicon system for use in rechargeable lithium batteries. J Power Sources 81–82:237–242
Courtney IA, McKinnon WR, Dahn JR (1999) On the aggregation of tin in SnO composite glasses caused by the reversible reaction with lithium. J Electrochem Soc 146:59–68
Mayo MJ (1997) High, and low temperature superplasticity in nanocrystalline materials. Nanostruct Mater 9:717–726
Wang W (2009) Silicon Based Nanocomposites as Lithium-ion Battery Anodes. PhD dissertation, Carnegie Mellon University
Idota Y, Kubota T, Matsufuji A, Maekawa Y, Miyasaka T (1997) Tin-based amorphous oxide: a high-capacity lithium-ion-storage material. Science 276:1395–1397
Hwang S-M et al (2001) Lithium insertion in SiAg powders produced by mechanical alloying. Electrochem Solid-State Lett 4:A97–A100
Kim H, Choi J, Sohn H-J, Kang T (1999) The insertion mechanism of lithium into Mg[sub 2]Si anode material for Li-ion batteries. J Electrochem Soc 146:4401–4405
Kim I-S, Kumta PN, Blomgren GE (2000) Si/TiN nanocomposites novel anode materials for Li-ion batteries. Electrochem Solid-State Lett 3:493–496
Kim I-S, Blomgren GE, Kumta PN (2004) Si-SiC nanocomposite anodes synthesized using high-energy mechanical milling. J Power Sources 130:275–280
Kim I-S, Blomgren GE, Kumta PN (2003) Nanostructured Si/TiB2 composite anodes for Li-ion batteries. Electrochem Solid-State Lett 6:A157–A161
Wang CS, Wu GT, Zhang XB, Qi ZF, Li WZ (1998) Lithium insertion in carbon-silicon composite materials produced by mechanical milling. J Electrochem Soc 145:2751–2758
Gross KJ, Wang JCF, Roberts GA (2004) Synthesis of carbon/silicon composites. US Patent 2004/137,327 (2004)
Kim I-S, Kumta PN (2004) High capacity Si/C nanocomposite anodes for Li-ion batteries. J Power Sources 136:145–149
Wilson AM, Reimers JN, Fuller EW, Dahn JR (1994) Lithium insertion in pyrolyzed siloxane polymers. Solid State Ionics 74:249–254
Yang J et al (2003) Si/C composites for high capacity lithium storage materials. Electrochem Solid-State Lett 6:A154–A156
Xie J, Cao GS, Zhao XB (2004) Electrochemical performances of Si-coated MCMB as anode material in lithium-ion cells. Mater Chem Phys 88:295–299
Holzapfel M et al (2005) Chemical vapor deposited silicon/graphite compound material as negative electrode for lithium-ion batteries. Electrochem Solid-State Lett 8:A516–A520
Holzapfel M, Buqa H, Scheifele W, Novak P, Petrat F-M (2005) A new type of nano-sized silicon/carbon composite electrode for reversible lithium insertion. Chem Commun 1566–1568
Dimov N, Fukuda K, Umeno T, Kugino S, Yoshio M (2003) Characterization of carbon-coated silicon: structural evolution and possible limitations. J Power Sources 114:88–95
Liu W-R et al (2005) Electrochemical characterizations on Si and C-coated Si particle electrodes for lithium-ion batteries. J Electrochem Soc 152:A1719–A1725
Yu M-F, Files BS, Arepalli S, Ruoff RS (2000) Tensile loading of ropes of single wall carbon nanotubes and their mechanical properties. Phys Rev Lett 84:5552
Krishnan A, Dujardin E, Ebbesen TW, Yianilos PN, Treacy MMJ (1998) Young’s modulus of single-walled nanotubes. Phys Rev B 58:14013
Wong EW, Sheehan PE, Lieber CM (1997) Nanobeam mechanics: elasticity, strength, and toughness of nanorods and nanotubes. Science 277:1971–1975
Roche S (2000) Carbon nanotubes: exceptional mechanical and electronic properties. Ann Chim Sci Matériaux 25:529–532
Zhao Q, Nardelli MB, Bernholc J (2002) Ultimate strength of carbon nanotubes: a theoretical study. Phys Rev B 65:144105
Demczyk BG et al (2002) Direct mechanical measurement of the tensile strength and elastic modulus of multiwalled carbon nanotubes. Mater Sci Eng A 334:173–178
Thess A et al (1996) Crystalline ropes of metallic carbon nanotubes. Science 273:483–487
Yao Z, Kane CL, Dekker C (2000) High-field electrical transport in single-wall carbon nanotubes. Phys Rev Lett 84:2941
Frank S et al (1998) Carbon nanotube quantum resistors. Science 280:1744–1746
Shu J, Li H, Yang R, Shi Y, Huang X (2006) Cage-like carbon nanotubes/Si composite as anode material for lithium ion batteries. Electrochem Commun 8:51–54
Wang W, Kumta PN (2007) Reversible high capacity nanocomposite anodes of Si/C/SWNTs for rechargeable Li-ion batteries. J Power Sources 172:650–658
Si Q et al (2010) A high performance silicon/carbon composite anode with carbon nanofiber for lithium-ion batteries. J Power Sources 195:1720–1725
Guo JC, Sun A, Wang CS (2010) A porous silicon-carbon anode with high overall capacity on carbon fiber current collector. Electrochem Commun 12:981–984
Lee J et al (2009) Effect of randomly networked carbon nanotubes in silicon-based anodes for lithium-ion batteries. J Electrochem Soc 156:A905–A910
Jang S-M, Miyawaki J, Tsuji M, Mochida I, Yoon S-H (2009) The preparation of a novel Si-CNF composite as an effective anodic material for lithium-ion batteries. Carbon 47:3383–3391
Yang J, Winter M, Besenhard JO (1996) Small particle size multiphase Li-alloy anodes for lithium-ionbatteries. Solid State Ionics 90:281–287
Yang J, Takeda Y, Imanishi N, Ichikawa T, Yamamoto O (2000) SnSbx-based composite electrodes for lithium ion cells. Solid State Ionics 135:175–180
Yang J, Takeda Y, Imanishi N, Yamamoto O (1999) Ultrafine Sn and SnSb0.14 Powders for lithium storage matrices in lithium-ion batteries. J Electrochem Society 146:4009–4013
Huggins R, Nix W (2000) Decrepitation model for capacity loss during cycling of alloys in rechargeable electrochemical systems. Solid State Ionics 6:57–63
Li H, Huang X, Chen L, Wu Z, Liang Y (1999) A high capacity nano-Si composite anode material for lithium rechargeable batteries. Electrochem Solid-State Lett 2:547–549
Beaulieu LY, Dahn JR (2000) The reaction of lithium with Sn-Mn-C intermetallics prepared by mechanical alloying. J Electrochem Soc 147:3237–3241
Gleiter H (1989) Nanocrystalline materials. Prog Mater Sci 33:223–315
Graetz J, Ahn CC, Yazami R, Fultz B (2003) Highly reversible lithium storage in nanostructured silicon. Electrochem Solid-State Lett 6:A194–A197
Maranchi JP, Hepp AF, Evans AG, Nuhfer NT, Kumta PN (2006) Interfacial properties of the a-Si/Cu:active–inactive thin-film anode system for lithium-ion batteries. J Electrochem Soc 153:A1246–A1253
Kim J-B, Lee H-Y, Lee K-S, Lim S-H, Lee S-M (2003) Fe/Si multi-layer thin film anodes for lithium rechargeable thin film batteries. Electrochem Commun 5:544–548
Kim Y-L et al (2003) Electrochemical characteristics of Co-Si alloy and multilayer films as anodes for lithium ion microbatteries. Electrochim Acta 48:2593–2597
Lee KL, Jung JY, Lee SW, Moon HS, Park JW (2004) Electrochemical characteristics of a-Si thin film anode for Li-ion rechargeable batteries. J Power Sources 129:270–274
Kim YL, Sun YK, Lee SM (2008) Enhanced electrochemical performance of silicon-based anode material by using current collector with modified surface morphology. Electrochim Acta 53:4500–4504
Yonezu I, Tarui H, Yoshimura S, Fujitani S, Nohma T (2004) Abstracts of the 12th International Meeting on Lithium Batteries, vol 58. Electrochemical Society, Nara, Japan, 2004
Lee JK, Smith KB, Hayner CM, Kung HH (2010) Silicon nanoparticles-graphene paper composites for Li ion battery anodes. Chem Commun 46:2025–2027
Chou SL et al (2010) Enhanced reversible lithium storage in a nanosize silicon/graphene composite. Electrochem Commun 2:303–306
Chan CK et al (2008) High-performance lithium battery anodes using silicon nanowires. Nat Nanotechnol 3:31–35
Yu DP et al (2001) Controlled growth of oriented amorphous silicon nanowires via a solid-liquid-solid (SLS) mechanism. Physica E 9:305–309
Kolb FM et al (2004) Analysis of silicon nanowires grown by combining SiO evaporation with the VLS mechanism. J Electrochem Soc 151:G472–G475
Chang JB et al (2006) Ultrafast growth of single-crystalline Si nanowires. Mater Lett 60:2125–2128
Zhang JG et al (2010) Vapor-induced solid–liquid–solid process for silicon-based nanowire growth. J Power Sources 195:1691–1697
Kim H, Han B, Choo J, Cho J (2008) Three-dimensional porous silicon particles for use in high-performance lithium secondary batteries. Angew Chem Int Ed 47:10151–10154
Zheng Y, Yang J, Wang JL, NuLi YN (2007) Nano-porous Si/C composites for anode material of lithium-ion batteries. Electrochim Acta 52:5863–5867
Xiao J et al (2010) Stabilization of silicon anode for Li-ion batteries. J Electrochem Soc 157:A1047–A1051
Ma H et al (2007) Nest-like silicon nanospheres for high-capacity lithium storage. Adv Mater 19:4067–4070
Magasinski A et al (2010) High-performance lithium-ion anodes using a hierarchical bottom-up approach. Nat Mat 9:353–358
Chen ZH, Christensen L, Dahn JR (2003) Large-volume-change electrodes for Li-ion batteries of amorphous alloy particles held by elastomeric tethers. Electrochem Commun 5:919–923
Chen ZH, Christensen L, Dahn JR (2003) Comparison of PVDF and PVDF-TFE-P as binders for electrode materials showing large volume changes in lithium-ion batteries. J Electrochem Soc 150:A1073–A1078
Chen ZH, Christensen L, Dahn JR (2004) Mechanical and electrical properties of poly(vinylidene fluoride-tetrafluoroethylene-propylene)/super-S carbon black swelled in liquid solvent as an electrode binder for lithium-ion batteries. J Appl Polym Sci 91:2958–2965
Liu WR, Yang MH, Wu HC, Chiao SM, Wu NL (2005) Enhanced cycle life of Si anode for Li-ion batteries by using modified elastomeric binder. Electrochem Solid-State Lett 8:A100–A103
Li J, Lewis RB, Dahn JR (2007) Sodium carboxymethyl cellulose – a potential binder for Si negative electrodes for Li-ion batteries. Electrochem Solid-State Lett 10:A17–A20
Dimov N, Xia Y, Yoshio M (2007) Practical silicon-based composite anodes for lithium-ion batteries: Fundamental and technological features. J Power Sources 171:886–893
Lestrie B, Bahri S, Sandu I, Roue L, Guyomard D (2007) On the binding mechanism of CMC in Si negative electrodes for Li-ion batteries. Electrochem Commun 9:2801–2806
Key B et al (2009) Real-time NMR investigations of structural changes in silicon electrodes for lithium-ion batteries. J Am Chem Soc 131:9239–9249
Buqa H, Holzapfel M, Krumeich F, Veit C, Novak P (2006) Study of styrene butadiene rubber and sodium methyl cellulose as binder for negative electrodes in lithium-ion batteries. J Power Sources 161:617–622
Xu YH, Yin GP, Ma YL, Zuo PJ, Cheng XQ (2010) Simple annealing process for performance improvement of silicon anode based on polyvinylidene fluoride binder. J Power Sources 195:2069–2073
Hochgatterer NS et al (2008) Silicon/graphite composite electrodes for high-capacity anodes: Influence of binder chemistry on cycling stability. Electrochem Solid-State Lett 11:A76–A80
Guo JC, Wang CS (2010) A polymer scaffold binder structure for high capacity silicon anode of lithium-ion battery. Chem Commun 46:1428–1430
Beattie SD, Larcher D, Morcrette M, Simon B, Tarascon JM (2008) Si electrodes for Li-ion batteries – a new way to look at an old problem. J Electrochem Soc 155:A158–A163
Zheng Y, Yang J, Tao L, Nuli YN, Wang JL (2007) Study of nano-porous Si/Graphite/C composite anode materials for Li-ion batteries. Chin J Inorg Chem 23:1882–1886
Chen LB, Xie XH, Xie JY, Wang K, Yang J (2006) Binder effect on cycling performance of silicon/carbon composite anodes for lithium ion batteries. J Appl Electrochem 36:1099–1104
Choi NS, Yew KH, Choi WU, Kim SS (2008) Enhanced electrochemical properties of a Si-based anode using an electrochemically active polyamide imide binder. J Power Sources 177:590–594
Liu G (2010) DOE hydrogen program and vehicle technologies program annual merit review and peer evaluation meeting. Department of Energy, Office of Energy Efficiency & Renewable Energy, Washington DC, 2010
Zhang JG, Liu J (2010) DOE hydrogen program and vehicle technologies program annual merit review and peer evaluation meeting. Department of Energy, Office of Energy Efficiency & Renewable Energy, Washington DC, 2010
Carmer JLG, Morales J, Sanchez L (2008) Nano-Si/cellulose composites as anode materials for lithium-ion batteries. Electrochem Solid-State Lett 11:A101–A104
Kulova TL, Skundin AM (2010) Elimination of irreversible capacity of amorphous silicon: direct contact of the silicon and lithium metal. Rus J Electrochem 46:470–475
Urbonaite S, Baglien I, Ensling D, Edstrom K (2010) Effect of ethanol-assisted electrode fabrication on the performance of silicon anodes. J Power Sources 195:5370–5373
Doh CH et al (2006) Synthesis of silicon-carbon by polyaniline coating and electrochemical properties of the Si-C vertical bar Li cell. Bull Korean Chem Soc 27:1175–1180
Choi NS et al (2006) Effect of fluoroethylene carbonate additive on interfacial properties of silicon thin-film electrode. J Power Sources 161:1254–1259
Chen LB, Wang K, Xie XH, Xie JY (2007) Effect of vinylene carbonate (VC) as electrolyte additive on electrochemical performance of Si film anode for lithium ion batteries. J Power Sources 174:538–543
Han GB, Ryou MH, Cho KY, Lee YM, Park JK (2010) Effect of succinic anhydride as an electrolyte additive on electrochemical characteristics of silicon thin-film electrode. J Power Sources 195:3709–3714
Baggetto L et al (2009) On the electrochemistry of an anode stack for all-solid-state 3D-integrated batteries. J Power Sources 189:402–410
Arie AA, Chang W, Lee JK (2010) Electrochemical characteristics of semi conductive silicon anode for lithium polymer batteries. J Electroceramics 24:308–312
Inose T, Watanabe D, Morimoto H, Tobishima SI (2006) Influence of glyme-based nonaqueous electrolyte solutions on electrochemical properties of Si-based anodes for rechargeable lithium cells. J Power Sources 162:1297–1303
Choi NS, Yew KH, Kim H, Kim SS, Choi WU (2007) Surface layer formed on silicon thin-film electrode in lithium bis(oxalato) borate-based electrolyte. J Power Sources 172:404–409
Lux SF et al (2010) Li-ion anodes in air-stable and hydrophobic ionic liquid-based electrolyte for safer and greener batteries. Int J Energy Res 34:97–106
Cui LF, Yang Y, Hsu CM, Cui Y (2009) Carbon – silicon core – shell nanowires as high capacity electrode for lithium ion batteries. Nano Lett 9:3370–3374
Yang Y et al (2010) New nanostructured Li2S/silicon rechargeable battery with high specific energy. Nano Lett 10:1486–1491
Arrebola JC et al (2009) Combining 5 V LiNi0.5Mn1.5O4 spinel and Si nanoparticles for advanced Li-ion batteries. Electrochem Commun 11:1061–1064
Lee K-L, Jung J-Y, Lee S-W, Moon H-S, Park J-W (2004) Electrochemical characteristics and cycle performance of LiMn2O4/a-Si microbattery. J Power Sources 130:241–246
Yin J et al (2006) Micrometer-scale amorphous Si thin-film electrodes fabricated by electron-beam deposition for Li-ion batteries. J Electrochem Soc 153:A472–A477
Baranchugov V, Markevich E, Pollak E, Salitra G, Aurbach D (2007) Amorphous silicon thin films as a high capacity anodes for Li-ion batteries in ionic liquid electrolytes. Electrochem Commun 9:796–800
Yang H et al (2007) Amorphous Si film anode coupled with LiCoO2 cathode in Li-ion cell. J Power Sources 174:533–537
Christensen J (2010) Modeling diffusion-induced stress in Li-Ion cells with porous electrodes. J Electrochem Soc 157:A366–A380
Gaines L, a.C., Roy in http://www.transportation.anl.gov/pdfs/TA/149.pdf
Author information
Authors and Affiliations
Corresponding author
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2012 Springer Science+Business Media, LLC
About this entry
Cite this entry
Zhang, JG. et al. (2012). Silicon-Based Anodes for Li-Ion Batteries . In: Meyers, R.A. (eds) Encyclopedia of Sustainability Science and Technology. Springer, New York, NY. https://doi.org/10.1007/978-1-4419-0851-3_496
Download citation
DOI: https://doi.org/10.1007/978-1-4419-0851-3_496
Publisher Name: Springer, New York, NY
Print ISBN: 978-0-387-89469-0
Online ISBN: 978-1-4419-0851-3
eBook Packages: Earth and Environmental ScienceReference Module Physical and Materials ScienceReference Module Earth and Environmental Sciences